Process for dyeing polyester fibers with nitrodiphenylamine dyestuff

ABSTRACT

POLYESTER FIBERS DYED WITH NITRODIPHENYLAMINE DYESTUFFS OF THE FORMULA 1-((3-(O2N-),4-(Z-NH-)PHENYL)-SO2-N(-R1)-A-N(-R2)-SO2-), 3-(O2N-),4-(Y-NH-)BENZENE IN WHICH A IS A SINGLE BOND OR A DIVALENT RADICAL AND R1 AND R2 ARE HYDROGEN, AN ALKYL, CYCLOALKYL, OR PHENYL AND Y AND Z ARE RESIDUES OF AN AMINE; ARE YELLOW DYESTUFFS PARTICULARLY SUITABLE FOR THE DYEING AND PRINTING OF SYNTHETIC FIBERS.

UnitedStates Patent Oflice 3,685,957 Patented Aug. 22, 1972 ABSTRACT OF THE DISCLOSURE Polyester fibers dyed with nitrodiphenylamine dyestuifs of the formula OgN NO:

I I a CROSS-REFERENCES TO RELATED APPLICATIONS This application is a continuation-in-part application of U.S. Ser. No. 698,099 filed Ian. 16, 1968.

BACKGROUND OF THE INVENTION It is known to employ dyestulfs of the general formula where R is hydrogen or phenyl for the dyeing of artificial fibers. However, the dyeings which are obtained are not completely satisfactory in their fastness properties and, in particular, do not possess the desired sublimation fastness.

This limitation is of particular importance in the dyeing of polyester fibers.

Polyester fibers present particular dyeing problems, arising at least in part out of the hydrophobic nature of such fibers. In the dyeing of polyester fibers, the class of dyes known as disperse dyestuffs has come to have the widest application. These dyestufls are essentially water-insoluble products applied in a finely divided condition from a dispersion. In the application of such dyestuffs, the dyeing difficulties associated with polyester fibers have been met by the development of special methods for the application of disperse dyes to the fibers. Of these methods, the one known as the Pad/Thermofix method has become of increasing infportance since it is particularly adapted for high-speed, continuous dyeing operations. In this method, a fabric is padded by passing it through an aqueous suspension of the dyestuif and squeezing the fabric between closely-set rollers in order to remove excess dye liquor. The dyestuff is only loosely attached to the fiber at this point. The dyestuff is then fixed on the fiber by subjecting the material to a short, intensive heat-treatment at elevated temperatures of the order of about 120220 C. It is evident that a dyestuif, in order to be suitable for application by this method, must be fast to sublimation or else it will wholly or partially volatilize from the fiber during the heat-treatment step.

SUMMARY OF THE INVENTION In accordance with the present invention, it has been SOiNHR found that valuable dyeings and printings are produced on fibrous materials of aromatic polyesters, especially polyethylene terephthalate, by using as dyestuffs nitrodiphenylamine compounds of the formula wherein A represents a single bond or a divalent radical which is an aliphatic straight or branched chain hydrocarbon of from 1 to 12 carbon atoms, such as ethylene, butylene, isobutylene, 3-methylhexylene, hexylene and the like (lower alkylene of from 1-12 carbon atoms), a metaor para-phenylene radical, a para-diphenylene radical or a radical of the formula in which B is CH 0, S0 8-8, or S; R, and R represent hydrogen, lower alkyl (from 1-7 carbon atoms) such as methyl, ethyl, propyl or butyl, hydroxyalkyl, (hydroxy lower alkyl such as hydroxymethyl, hydroxyethyl, hydroxypropyl or hydroxybutyl), cycloalkyl of from 3 to 8 carbon atoms such as cyclohexyl and cyclopentyl or phenyl, or when A is lower alkylene R and R may also be taken together and form an alkylene group so that A+R +R together contain 3-6 carbon atoms and preferably, 4; Y and Z can be the same or different and are selected from the group consisting of lower alkyl of from 1-7 carbon atoms, cycloalkyl of from 3-8 carbon atoms such as cyclopentyl, and cyclohexyl and each of said lower alkyl and cycloalkyl may be substituted with lower alkoxy, hydroxy, halogen, or trifluoromethyl, and the cycloalkyl may further contain 1-2 lower alkyl groups (of from l-S carbon atoms) such as methyl, propyl and the like; the radical of the formula Ram wherein n is l, 2 or 3 and R and R are hydrogen, lower alkyl (1-7 carbon atoms) such as methyl, ethyl, propyl or butyl, hydroxy lower alkyl of from 1-7 carbon atoms; such as hydroxymethyl, hydroxypropyl, hydroxybutyl and the like, lower alkoxy (of from 1 to 7 carbon atoms) such as methoxy, ethoxy, propoxy or butoxy, hydroxy lower alkoxy of from 1 to 7carbon atoms, such as hydroxymethoxy, Z-hydroxypropoxy, hydroxy isobutoxy, Z-hydroxypentoxy and the like; halogen such as chlorine or bromine, hydroxyl, trifluoromethyl or acylamino such as lower alkanoylamino of from 1 to 7 carbon atoms, such as acetylamino, propionoylamino, pentanoylamino and the like; or aroylamino, such as benzoylamino and the like; carbamoyl or sulfamoyl, and R and R, can be in the ortho, meta or para positions.

The aromatic rings represented by the symbol A can be substituted by the same substituents as are recited in the definition of R and R The nitrodiphenylamines employed in the present invention are prepared by combining compounds of the formula wherein A, R and R have the meanings given above and X is halogen, preferably chlorine, with an aromatic amine of the formulae NH and NH1 where R and R have the meanings ascribed above and can be the same or different.

Instead of the aromatic amine reactants mentioned in the preceding paragraph, certain aliphatic amines, (alkylamines of from 2-10 carbon atoms) can also be employed. Examples of these amines are 3-methoxypropylamine, 2-hydroxybutylamine and 3-chloropropylamine and especially cyclohexylamine. The dyestuffs obtained when these amines are employed as reactants produce bright greenish fellow dyeings o fexcellent sublimation fastness and good light fastness.

The compounds of the formula OzN N are prepared by acylating a primary or secondary diamine of the formula where R R and A have the meanings given above with a suitable acylating agent, such as 3-nitro-4-chlorobenzenesulfonyl chloride in aqueous medium or with solvent with or without heating and, preferably, in the presence of a proton acceptor.

The preferred nitrodiphenylamines employed in the present invention are those wherein A is a straight or branched chain alkylene of from 2-6 carbon atoms, and especially ethylene, methylethylene, and propylene: R and R are hydrogen or hydroxy lower alkyl of from 2 to 6 carbon atoms, and especially hydrogen, or hydrogen for one of R and R and hydroxy lower alkyl for the other; Y and Z the same or different and phenyl, monoalkylphenyl, monoalkoxyphenyl, monohydroxyalkylphenyl wherein the side chain contains from 2-6 carbon atoms and is attached to the o, m, or p position; and cyclohexyl; and especially phenyl.

Throughout the specification the symbol refers to a phenyl moiety and to a cyclohexyl moiety.

For dyeing, the said dyestuffs are preferably used in a finely divided form and the dyeing is carried out in the presence of a dispersing agent, such as sulphite cellulose or waste liquor or a combination of different wetting and dispersing agents. Before dyeing, it is generally of advantage to convert the dyestuff or dyestuffs to be used into a dyestuff preparation which contains a dispersing agent and the finely divided dyestuff(s) in such a form as to yield a fine dispersion when the preparation is diluted with water. Dyestuff preparations of this kind can be made by known methods, for example, by grinding the dyestuff(s) either in dry or wet form with or without the addition of a dispersing agent.

The dyestuffs used in the invention are especially suitable for dyeing by the so-called thermofixation or Pad/ Thermofix method, in which the fabric to be dyed is impregnated advantageously at a temperature not exceeding 60 C. with an aqueous dispersion of the dyestuff, which may contain 1 to 50% of urea and a thickening agent, especially sodium alginate, and the fabric is squeezed in the usual manner. The squeezing is prefer- 4 ably carried out so that the goods retain 50 to of their weight of dye liquor.

The dyestutf is fixed by subjecting the impregnated fabric to a heat treatment at temperatures above 100 C., for example, at a temperature ranging from 220 C., it being of advantage to dry the fabric prior to this treatment, for example, in a current of warm air.

The thermofixation mentioned above is of special interest for the dyeing of mixed fabrics of polyester fibers and cellulose fibers, especially cotton. In this case, in addition to the dyestuff to be used in the process of the invention, the padding liquor contains a dyestuff suitable for dyeing cotton, for example, a direct dyestuff or vat dyestuff, or a so-called reactive dyestuff, i.e. a dyestuff capable of being fixed on cellulose fibers with the formation of a chemical bond, for example, a dyestuff containing a chlorotriazine or chlorodiazine residue. In the latter case it is of advantage to add to the padding liquor an agent capable of binding acid, for example, an alkali carbonate, alkali phosphate, alkali borate or alkali perborate, or a mixture of two or more of these agents. When vat dyestuffs are used, the padded fabric must be treated, after the heat treatment, with an aqueous alkaline solution of a reducing agent of the kind used in vat dyeing.

The dyeings produced on polyester fibers by the process of the invention are advantageously given an aftertreatment, for example, by heating them with an aqueous solution of a non-ionic detergent.

Instead of applying the dyestuffs in the process by impregnation, they may be applied by printing. For this purpose, a printing color is used which, in addition to the usual printing assistants, such as wetting and thickening agents, contains the finely dispersed dyestuff, if desired, in admixture with one of the aforesaid cotton dyestuffs, and, if desired, in the presence of urea and/or an agent capable of binding acid.

There are obtained by the practice of the present invention strong yellow dyeings or prints of attractive shade and good color build-up having excellent fastness properties, especially a good fastness to sublimation and to light. The introduction of permanent press fabrics has lent still further emphasis to the importance of sublimation fastness since the processes involved in the preparation of such fabrics require the curing at elevated temperatures for prolonged periods of the resin finishes applied for the achievement of permanent press characteristics.

The term polyester defines synthetic polymeric polyesters, such as the highly polymeric linear polyesters, the molecules of which have recurring monomeric units connected by ester linkages. Dibasic acids, for example, aromatic acids, such as terephthalic acid, diphenyl-4,4'-dicarboxylic acid and/or diphenylsulfone-4,4'-dicarboxylic acid and dihydroxy compounds, for example, glycols, such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and/ or butylene glycol, as well as other diols, such as 1,4-bis (hydroxymethyl)-hexahydrobenzene, 1,4-cyclohexandiol can be used as the monomers to form the polymeric polyesters, and preferably the condensation product of terephthalic acid and ethylene glycol or 1,4- bis (hydroxymethyl) hexahydrobenzene. Typical commercial examples of such fibers are Dacron, Terylene, Fortrel, Trevira, Terlanca, Kodel, Vicron, etc. They are disclosed, for example, in US. Pat. No. 2,901,466 and British Pats. Nos. 578,079; 579,462; 588,497 and 596,688.

The present invention is, of course, equally applicable to the dyeing of blends of polyester fibers and cellulosic fibers. The latter term includes native cellulose, such as linen or, more particularly, cotton, as well as regenerated cellulose, such as viscose of cuprammonium rayon.

The following examples illustrate the invention.

Example 1 50 g. by weight of N,N' ethylene bis 4 chloro- 3 nitrobenzene 1 sulfonamide, 22 g. of aniline, 50 g. of anhydrous sodium acetate, and 650 g. of 95% ethanol are stirred for 24 hours at 130 C. in an autoclave. The reaction mass is cooled, filtered and washed with ethanol. The collected precipitate is washed with hot water, filtered, and washed until free of salts. The product, N,N'- ethylene bis 4 phenylamino 3 nitrobenzenc 1- sulfonamide, obtained in a yield of 45 g., gives yellow dyeings on polyester fibers.

The N,N' ethylene bis 4 chloro 3 nitrobenzenel-sulfonamide employed above is prepared in the following manner: 6 g. by weight of ethylenediamine are dissolved in 60 g. of water at 2 C. To this solution there are added over a period of minutes, with stirring, 73 g. of a wet paste containing 51 parts of 4 chloro 3 nitrobenzene 1 sulfonyl chloride and the balance water. The mixture is heated, with agitation, during 30 minutes, to 60 C. The neutrality is then maintained over 2 hours by the gradual addition of 16.5 g. of a 50% by weight solution of sodium hydroxide in water. The precipitate is recovered by filtration and washed thoroughly with water. 45 g. by weight of product are obtained, recrystallized from ethanol and collected as a colorless crystalline powder melting at 221-2225 C.

Example 2 51.4 g. by weight of N,N-methylethylene-bis-4-chloro-3-nitrobenzene-l-sulfonamide and 22.5 g. of aniline are added to a solution of 110 g. sodium acetate in 73 g. water at 90 C. and heated for hours at 115 to 120 C. with stirring. The reaction mixture is diluted with 80 g. of water and filtered. The solids are washed thoroughly with hot water and dried. 60.5 g. of N,N'- methylethylene bis-4-phenylamino-3-nitrobenzene-l-sulfonamide giving yellow shades on polyester fibers are obtained.

When N,N"-ethylene-bis-4-chloro-3nitrobenzene-l-sulfonamide and p-aminophenethyl alcohol, 4-aminobenzanilide, p-aminophenol or 2(2'-aminoethoxy) ethanol is used in place of N,N'-methylethylene-bis-4-chloro-3-nitrobenzene-l-sulfonamide and aniline respectively, in equivalent amounts, there is obtained the corresponding nitrodiphenylamine dyestulf.

Example 3 54.6 g. of N,N'-p-phenylene-bis-4-chloro-3-nitrobenzene-l-sulfonamide and 22.5 g. of aniline are added to a solution of 110 g. sodium acetate in 73 g. water at 90 C. and heated for 20 hours at 120 C. with stirring. The reaction mixture is diluted with 80 g. of water and filtered. The solids are washed thoroughly with hot water and dried. 59 g. of N,N'-p-phenylene-bis-4-phenylamino- 3-nitrobenzene-l-sulfonamide, giving yellow shades on polyester fibers are obtained.

- The N,N'-p-phenylene-bis-4-chloro 3 nitrobenzene-lsulfonamide employed above is prepared in the following manner: To a stirred mixture of 11 g. by weight of p-phenylene-diamine, 24 g. of anhydrous sodium acetate and 45 g. of acetone there are added, with external cooling, at 10-25 C., 73 g. of a wet paste containing 51 g. of 4-chloro-3-nitrobenzene-l-sulfonyl chloride and the balance water. The reaction mass is heated and a temperature of 55 C. is maintained for 30 minutes. The reaction mass is diluted with water, filtered, the precipitate washed with ethanol, and then with hot water.

Example 4 50 g. by weight of N,N'-ethylene-bis-4-chloro-3-nitrobenzene-l-sulfonamide and 24 g. of cyclohexylamine are added to a solution of 120 g. of sodium acetate in g. of water at C. and heated for 18 hours at 116 C. with stirring. The reaction mixture is diluted with 200 g. of water and filtered. The solids are washed thoroughly with hot water and dried. 58 g. of N,N-ethylene-bis-4- cyclohexylamino 3 nitrobenzene-l-sulfonamido giving greenish-yellow shades on polyester fibers are obtained.

Example 5 51.3 g. by weight of N,N-(1,3-propylene-bis)-4-chloro-3-nitrobenzene-l-sulfonamide and 22 g. of 3-methoxypropylamine are stirred in a solution of 120 g. of sodium acetate in 80 g. of water at 116 C. for 18 hours. The reaction mixture is diluted with 250 g. of water, cooled until the oily product solidifies, and filtered. The solids are thoroughly washed with water, and then with methanol. 52.5 g. of N,N'-(1,3-propylene-bis)-4-w-methoxypropylamino 3 nitrobenzene-l-sultonarnide giving greenish-yellow shades on polyester fibers are obtained.

When N-p-hydroxyethyl-N,N'-p-phenylene-bis-(4-chloro-3-nitrobenzene)-l-sulfonamide and p-aminophenethyl alcohol, or N-B-hydroxyethyl-N,N-ethylene-bis-(4-chloro- 3-nitrobenzene)-l-sulfonamide and aniline, or N,N-;3- hydroxyethyl-N,N'-ethylene-bis(4-chloro-3-nitrobenzene)- l-sulfonamide and aniline, or bis-(3-nitro-4-chlorobenzenesulfonamido) p,p diphenylsulfide and aniline, or bis (3-nitro-4-chlorobenzenesulfonamido)-p,p-diphenyldisulfide and aniline, or bis-(3-nitro-4-chlorobenzenesulfonamido)-p,p'-diphenylsulfone and aniline, or N,N'- ethylene-bis-4-chloro 3 nitrobenzene-l-sulfonamide and m-aminophenol are used in place of an equivalent amount of N,N-(1,3-propylene-bis)-4-chloro 3 nitrobenzene-lsulfonamide and 3 methoxypropylamine respectively, there is obtained the corresponding nitrodiphenylamine dyestuff.

Example 6 The dyes listed below are prepared by the method of Example 2 or 5 as indicated, opposite each compound. They give yellow dyeings on polyester fibers characterized by good penetration and excellent fastness to light and sublimation.

TABLE Prepared by procedure of Example N 0.:

2(a)...'."... OaN

OrN

TABLE-Continued N20 OCH:

OOH:

HaCO

Example 7 15 g. of N,N-ethy1ene-bis-4-phenylamino-3-nitro-benzene-l-sulfamide (Example 1) are brought to a state of fine dispersion by milling in a ball mill with parts of the condensation product of naphthalene-Z-sulfonic acid with formaldehyde and 75 g. of water.

An aqueous preparation containing 67 g. of the above dyestutf dispersion and 0.5 g. of sodium alginate per liter is padded onto fabric of polyethylene terephthalate fiber and squeezed to 65% pick-up. The padded material is then air dried and subsequently heat dried at 220 C. for 1 minute. The dyed fabric is scoured for 5 minutes at the boil in a solution containing 3% of sodium di-iso-butylnaphthalene monosulfate and 5% sodium carbonate and then dried. A yellow dyeing is obtained, characterized by good penetration and excellent fastness to light and sublimation. Similar results are obtained when poly(1,4-cyclohexylene-dimethylene terephthalate) is used in place of polyethylene terephthalate fiber in the above example.

Example 8 The procedure of Example 7 is repeated, except that g. each of the yellow dyes listed in Examples 2-6 are employed for the dispersion. A yellow dyeing is obtained in each instance characterized by good penetration and excellent fastness to light and sublimation.

The procedure of Example 7 is repeated, except that a total of 15 g. of each of the dyes of Examples 2 and 3 are employed. Satisfactory dyeings are obtained. Combinations of the other dyestuffs as mentioned in Examples 2-6 can be similarly employed.

I claim:

1. Polyester fiber dyed with a compound of the formula OzN wherein A is a single bond, an aliphatic straight-chained hydrocarbon of 1-12 carbon atoms, an aliphatic branched chained hydrocarbon of 1-12 carbon atoms, meta-phenylene, para-phenylene, para-diphenylene, or a radical of the formula 0- -6- in which B is CH 0, S, 8-8, or S0 R and R are each lower alkyl, hydroxyalkyl, cycloalkyl, phenyl or hydrogen for one of R and R when A is alkylene, R and R may be taken together and form an alkylene; Y and Z are individually cyclohexyl, a radical of the formula Run) or of the formula wherein n is 1, 2 or 3 and R and R are individually hydrogen, lower alkyl, hydroxy lower alkyl, hydroxy lower alkoxy, lower alkoxy, halogen, trifluoromethyl, acylamino, carbamoyl, or sulfamoyl.

2. A polyester fiber of claim 1 wherein A is a straight or branched chain alkylene of from 2 to 6 carbon atoms; 'R and R are each hydroxy lower alkyl of from 2 to 6 carbon or hydrogen for one of R and R and Y and Z are phenyl, monoalkylphenyl, monoalkoxyphenyl or monohydroxyalkylphenyl wherein the side chain con tains from 2 to 6 carbon atoms, or cyclohexyl.

3. Process for coloring polyester fiber which comprises applying to fibrous material of synthetic polyester an aqueous dispersion of a compound of claim 1.

References Cited UNITED STATES PATENTS 2,080,704 5/1937 Fischer et al. 260397.7 3,239,543 3/ 1966 Bement 260--397.7 3,537,811 11/1970 Stingl 8-179 X GEORGE F. LESMES, Primary Examiner T. I. HERBERT, 111., Assistant Examiner US. Cl. X.R. 260-397] 

